JP3275157B2 - Glass fiber reinforced thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to a novel glass fiber reinforced thermoplastic resin composition comprising a glass fiber reinforced polycarbonate resin and a liquid crystal polymer having a special phenyl end group.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are excellent in heat resistance, impact resistance and mechanical strength, and are widely used as highly functional resins, that is, engineering plastics. Furthermore, blends with various resins utilizing the properties of aromatic polycarbonates are known.

[0003] For example, a patent application (name of the invention: resin composition, application number Japanese Patent Application No. Hei. 359735).

Here, a resin composition containing a polycarbonate having a phenol terminal group has a higher impact resistance and flexural modulus than a similar resin composition containing a normal polycarbonate (hereinafter abbreviated as PC). It is disclosed that it is superior in the point. This is due to the good compatibility between LCP and polycarbonate having phenol end groups.

However, the modulus of elasticity of a molded article made of LCP / PC resin can be reduced even in a case where such an LCP is added in a specific use, for example, in a thin housing or case required for a portable device. Is still not enough.

[0006]

SUMMARY OF THE INVENTION The present invention provides a thermoplastic resin composition comprising an aromatic polycarbonate, a liquid crystal polyester, and a glass filler, which simultaneously achieves a high elastic modulus and good impact resistance. The task is to

[0007]

The object of the present invention is to provide:
45 to 5 parts by weight of thermotropic liquid crystal polyester resin, and B) glass fiber and / or glass flake 5
And the equivalent ratio (I) / (II) of C) phenolic terminal group (I) and non-phenolic terminal group (II) is 1/40 parts by weight.
Polycarbonate 1 obtained by melt-polymerizing an aromatic dihydroxy compound and a carbonic acid diester, which is 19 or more
And a glass fiber reinforced thermoplastic resin composition containing 5 to 90 parts by weight.

The present inventors have found that a thermotropic liquid crystal polyester is blended with a polycarbonate having a specific structure obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester, ie, a polycarbonate having a terminal group having the above equivalent ratio. Can significantly improve the compatibility between the thermotropic liquid crystal polyester and polycarbonate.The thermoplastic resin of the present invention has no delamination and combines the reinforcing effect of the thermotropic liquid crystal polyester with the excellent properties of polycarbonate. The composition was completed.

The component (B) used in the present invention is a glass fiber having an average fiber diameter of 10 μm or less, preferably 8 μm or less, particularly preferably 6 μm or less. When the average fiber diameter exceeds 10 μm, the effect of the present invention is not exhibited.
As long as the average fiber diameter is 10 μm, any of commercially available glass fibers available as chopped glass, roving glass, milled glass and the like can be used. The composition of the glass is not particularly limited, but is preferably E glass. In addition, such a glass component is not limited to the above-described fiber shape, and may be a flake shape.

The component (C) polycarbonate used in the present invention is obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester, and has a phenolic terminal group (I) and a non-phenolic terminal group (I). II)
Is an equivalent ratio (I) / (II) of 1/19 or more, preferably 1/10 or more, and particularly preferably 1/5 or more. When the ratio is less than 1/19, compatibility with the thermotropic liquid crystal polyester is not improved, and delamination occurs,
It is not preferable because the mechanical strength is reduced.

Preferably, the phenolic terminal group (I) has the following formula:

[0012]

Embedded image And the non-phenolic terminal group (II) is

[0013]

Embedded image Indicated by Here, in the above formula, R ¹ and R ² are each independently a hydrogen atom, a linear or branched, unsubstituted or halogen atom having 20 or less carbon atoms, preferably substituted by a fluorine, chlorine, or bromine atom. Shows an alkyl group.

The adjustment of the equivalent ratio of the terminal groups of the polycarbonate can be easily carried out by changing the molar ratio of the aromatic dihydroxy compound and the carbonic acid diester as raw materials when producing the polycarbonate by melt polymerization.

For example, when bisphenol A is used as the aromatic dihydroxy compound and diphenyl carbonate is used as the carbonic acid diester, the terminal groups of the polycarbonate are a phenolic residue derived from bisphenol A and a phenyl group derived from diphenyl carbonate;
When the molar ratio of bisphenol A is increased, the equivalent ratio (I) / (II) of the phenolic terminal group (I) and the non-phenolic terminal group (II) in the produced polycarbonate increases.

Further, the polycarbonate of the present invention may be branched. Such branched polycarbonates are obtained as branched thermoplastic random branched carbonates by reacting a polyfunctional aromatic compound with a diphenol and / or a carbonate precursor.

In a polycarbonate generally used conventionally, particularly a polycarbonate obtained by a method of reacting an aromatic dihydroxy compound such as bisphenol A with phosgene (particularly an interface method), a phenolic terminal group (I) and a non-phenol The equivalent ratio (I) / (II) of the terminal group (II) is less than 1/19, which is not preferred.

The method of producing the polycarbonate of the present invention is known per se, and is a method of synthesizing a polycarbonate by a transesterification reaction of an aromatic dihydroxy compound and a carbonic acid diester in a molten state.

The aromatic dihydroxy compound is not particularly limited, and various known compounds can be used. As an example, the following expression

[0020]

Embedded image (Where ^Ra and ^Rb are each independently a halogen or a monovalent hydrocarbon group, and X is -C ( ^Rc ) ( ^Rd )
—, —C (＝ R ^e ) —, —O—, —S—, —SO— or —SO ₂ —, and R ^c and R ^d are each independently a hydrogen atom or a monovalent hydrocarbon group. R ^e is a divalent hydrocarbon group, and p and q each independently represent an integer of 0 to 4. ), For example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4 -Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1- Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-t-butylphenyl) propane and 2,2-bis (4-hydroxy-3-bromophenyl) propane; 1,1-bis (4-hydroxyphenyl) Bis (hydroxyaryl) cycloalkanes such as cyclopentane and 1,1- (4-hydroxyphenyl) cyclohexane; 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethylphenyl ether 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,
Dihydroxy diaryl sulfides such as 3'-dimethylphenyl sulfide; dihydroxy diaryl sulfoxides such as 4,4'-dihydroxy diphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide; 4,4'-dihydroxy Diphenyl sulfone,
Examples include, but are not limited to, dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. In addition to the above, as the aromatic dihydroxy compound, the following general formula

[0021]

Embedded image (Where R ^f is independently a hydrocarbon group having 1 to 10 carbon atoms or a halogen compound or a halogen atom, and m is an integer of 0 to 4), for example, resorcinol , And 3-methylresorcinol, 3-
Ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin, 2,3,4,6-tetrafluororesorcin, 2,3,4,6 -Substituted resorcinols such as -tetrabromoresorcin; catechol; hydroquinone and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumyl Hydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,
Substituted hydroquinones such as 5,6-tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone, and the following formula

[0022]

Embedded image 2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi- [1H-indene] -7,7'-diol represented by Can also be used.

These aromatic dihydroxy compounds may be used alone or in combination of two or more.

There are no particular restrictions on the carbonic diester. For example, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl Examples include, but are not limited to, carbonate, dicyclohexyl carbonate, and the like. Preferably, diphenyl carbonate is used.

These carbonates may be used alone or in combination of two or more.

The carbonic acid diester may contain a dicarboxylic acid or a dicarboxylic acid ester. Examples of dicarboxylic acids and dicarboxylic acid esters include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl terephthalate and diphenyl isophthalate; succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin, and the like. Aliphatic dicarboxylic acids such as acid, decandioic acid, dodecandioic acid, diphenyl sebacate, diphenyl decandioic acid, diphenyl dodecandioic acid; cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diphenyl cyclopropanedicarboxylate, 1 2,2-cyclobutanedicarboxylic acid di Eniru, 1,3-cyclobutane dicarboxylic acid, diphenyl 1,2-cyclopentane dicarboxylic acid, diphenyl 1,3-cyclopentane dicarboxylic acid, diphenyl 1,2-cyclohexane dicarboxylic acid diphenyl, 1,
Alicyclic dicarboxylic acids such as diphenyl 3-cyclohexanedicarboxylate and diphenyl 1,4-cyclohexanedicarboxylate can be mentioned.

These dicarboxylic acids or dicarboxylic acid esters may be used alone or in combination of two or more. The dicarboxylic acid or dicarboxylic acid ester is contained in the diester carbonate in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.

In producing the polycarbonate, a polyfunctional compound having three or more functional groups in one molecule can be used together with the aromatic dihydroxy compound and the carbonic acid diester. As these polyfunctional compounds, compounds having a phenolic hydroxyl group or a carboxyl group are preferable, and compounds having three phenolic hydroxyl groups are particularly preferable.

Specific examples of preferred compounds include 1,1,1-
Tris (4-hydroxyphenyl) ethane, 2,2 ', 2 "-tris (4-hydroxyphenyl) diisopropylbenzene,
α-methyl-α, α ′, α′-tris (4-hydroxyphenyl) -1,4-diethylbenzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-tri Isopropylbenzene, phloroglysin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane-2,1,3,5-tri (4-hydroxyphenyl) benzene, 2,2-bis -[4,4- (4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid and the like.

Particularly preferably, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like are used. The polyfunctional compound is preferably used in an amount of 0.03 mol or less, more preferably 0.001 to 0.02 mol, particularly preferably 0.001 to 0.01 mol, per mol of the aromatic dihydroxy compound. Used in quantity.

When producing polycarbonate,
The resulting polycarbonate has the following formula

[0032]

Embedded image (Here, the aromatic ring or the chromanyl group may be substituted with a halogen or an alkyl group having 1 to 9 carbon atoms.)
Compounds into which one or more of the terminal groups can be introduced can be further used. Examples of the compound capable of introducing a hydroxyl group represented by (1) include diol compounds such as bisphenol A. Examples of the compound capable of introducing the phenoxy group represented by (2) include phenol and diphenyl carbonate; and examples of the compound capable of introducing the pt-butylphenoxy group represented by (3) include pt-butylphenol and p-butylphenol. -T-
P-cumylphenol as a compound capable of introducing a p-cumylphenoxy group (p-phenylisopropylphenoxy group) represented by (4);
Examples thereof include p-cumylphenylphenyl carbonate, p-cumylphenyl carbonate, and the like.
The chromanylphenoxy group represented by (5) in the above formula includes the following formula:

[0033]

Embedded image And a chromanylphenoxy group. As a compound into which the group represented by (5-1) can be introduced
2,2,4-trimethyl-4- (4-hydroxyphenyl) chroman, 2,2,4,6-tetramethyl-4- (3,5-dimethyl-4-hydroxyphenyl) chroman, 2,3,4 -Trimethyl-2-ethyl-4- (3-nonyl-4-hydroxyphenyl) -7-nonyl-
Chroman, 2,2,4-trimethyl-4- (3,5-diethyl-4-hydroxyphenyl) -6-ethylchroman, 2,2,4,6,8-pentamethyl-4- (3,5-dimethyl -4-hydroxyphenyl) chroman, 2,2,4-triethyl-3-methyl-4- (4-hydroxyphenyl) chroman, 2,2,4-trimethyl-4- (3-bromo-
4-Hydroxyphenyl) chroman, 2,2,4-trimethyl-4
-(3-bromo-4-hydroxyphenyl) -6-bromochroman, 2,2,4-trimethyl-4- (3,5-dibromo-4-hydroxyphenyl) -6-bromochroman, 2,2,4-trimethyl -Four-
(3,5-dibromo-4-hydroxyphenyl) -6,8-dibromochroman and the like.
2,4-trimethyl-4- (4-hydroxyphenyl) chroman is preferable; as a compound into which the group represented by (5-2) can be introduced, 2,2,3-trimethyl-3- (4-hydroxyphenyl) Chroman, 2,2,3,6-tetramethyl-3- (3,5-dimethyl-4-hydroxyphenyl) chroman, 2,3,4-trimethyl-2-ethyl-3- (3-nonyl-4- Hydroxyphenyl) -7-
Nonyl-chroman, 2,2,3-trimethyl-3- (3,5-diethyl
-4-hydroxyphenyl) -6-ethyl-chroman, 2,2,3,
6,8-pentamethyl-3- (3,5-dimethyl-4-hydroxyphenyl) chroman, 2,2,3-triethyl-3-methyl-3- (4-hydroxyphenyl) chroman, 2,2,3- Trimethyl-3- (3
-Bromo-4-hydroxyphenyl) -6-bromochroman,
2,2,3, -trimethyl-3- (3,5-dibromo-4-hydroxyphenyl) -6-bromochroman, 2,2,3-trimethyl-3- (3,
5-dibromo-4-hydroxyphenyl) -6,8-dibromochroman, among which 2,2,3-trimethyl-3- (4-hydroxyphenyl) chroman is particularly preferred; Compounds into which the group represented by 3) can be introduced include 2,4,4-trimethyl-2- (2-hydroxyphenyl) chroman and 2,4,4,6-tetramethyl-2- (3,5-dimethyl 2-Hydroxyphenyl) chroman, 2,3,4-trimethyl-4-ethyl-2- (3,5-dimethyl-2-hydroxyphenyl) -7-nonyl-chroman, 2,4,4-trimethyl-2 -(3,5-dimethyl-2-
Hydroxyphenyl) -6-ethylchroman, 2,4,4,6,8-
Pentamethyl-2- (3,5-dimethyl-2-hydroxyphenyl) -6-ethylchroman, 2,4,4-trimethyl-2- (3-bromo-2-hydroxyphenyl) chroman, 2,4,4- Trimethyl-2- (3-bromo-2-hydroxyphenyl) -6-bromochroman, 2,4,4-trimethyl-2- (3,5-dibromo-2-hydroxyphenyl) -6-bromochroman, 2,4, 4-trimethyl-
Examples thereof include 2- (3,5-dibromo-2-hydroxyphenyl) -6,8-dibromochroman, and among them,
4,4-trimethyl-2--2- (hydroxyphenyl) chroman is preferable; as a compound into which the group represented by (5-4) can be introduced, 2,4,4-trimethyl-2- (4-hydroxyphenyl) Chroman, 2,4,4,6-tetramethyl-2- (3,5-dimethyl-4-hydroxyphenyl) chroman, 2,4,4-triethyl-2- (4-hydroxyphenyl) chroman, 2,3 , 4-Trimethyl-4-ethyl-2- (3,5-dimethyl-4-hydroxyphenyl) -7-nonyl-chroman, 2,4,4-trimethyl-2- (3,5
-Diethyl-4-hydroxyphenyl) -6-ethyl-chroman, 2,4,4,6,8-pentamethyl-2- (3,5-dimethyl-4-hydroxyphenyl) -6-ethylchroman, 2,4 , 4-Trimethyl-2- (3-bromo-4-hydroxyphenyl) chroman, 2,
4,4-trimethyl-2- (3-bromo-4-hydroxyphenyl)
-6-bromochroman, 2,4,4-trimethyl-2- (3,5-dibromo-4-hydroxyphenyl) -6-bromochroman, 2,4,4-
Trimethyl-2- (3,5-dibromo-4-hydroxyphenyl)
-6,8-Dibromochroman and the like can be mentioned, and among them, 2,4,4-trimethyl-2- (4-hydroxyphenyl) chroman is particularly preferable.

In the above, the aromatic or aliphatic ring is
It may be further substituted with a halogen or an alkyl group having 1 to 9 carbon atoms. These compounds may be used alone or in combination of two or more.

Preferably, the aromatic dihydroxy compound 1
1.00 to 1.30 mol, particularly 1.01 to 1.
The two are reacted in the presence of a catalyst using an amount of 1.20 moles of carbonic acid diester.

As the catalyst, for example, the applicant of the present invention
The compounds proposed in the specification of 4-175368 can be used. By way of example, it is preferred to use (a) organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides or alcoholates of metals such as alkali metals and alkaline earth metals. Specific examples of these compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, and stearin. Sodium acid, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride,
Sodium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt, dipotassium salt, dilithium salt of bisphenol A, Phenol sodium salt, potassium salt, lithium salt, etc .; calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, Examples include, but are not limited to, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, strontium stearate, and the like. These compounds may be used alone or in combination of two or more. These alkali metal compounds and / or alkaline earth metal compounds are preferably 10 ^-8 to 10 ^-3 mol, more preferably 10 ^-7 to 10 ^-6 mol, particularly preferably 1 mol of the aromatic dihydroxy compound. 10 ^-7
Used in an amount of ８8 × 10 ⁻⁷ mol.

As the catalyst, together with the alkali metal compound and / or the alkaline earth metal compound, (b)
A basic compound may be used. Examples of the basic compound include, for example, nitrogen compounds, specifically, ammonium having an alkyl, aryl, or araryl group, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Hydroxides; tertiary amines such as trimethyleneamine, triethylamine, dimethylbenzylamine and triphenylamine; secondary and primary having alkyl groups such as methyl group and ethyl group, and aryl groups such as phenyl group and toluyl group. Amine; ammonia; tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetramethylammonium And the like can be mentioned basic salts such as tiger tetraphenylborate, but are not limited to. Of these, ammonium hydroxides are particularly preferred. These basic compounds may be used alone or in combination of two or more.

In the present invention, by using a combination of the above-mentioned (a) an alkali metal compound and / or an alkaline earth metal compound and (b) a nitrogen-containing basic compound as a catalyst, a high-molecular-weight polycarbonate can be produced at a high level. It can be obtained by polymerization activity.

Alternatively, as the catalyst, (a) an alkali metal compound and / or an alkaline earth metal compound;
A combination of a nitrogen-containing basic compound and (c) at least one of boric acid and boric acid ester can be used. When a catalyst comprising such a combination is used, (a) an alkali metal compound and / or an alkaline earth metal compound is used in the above-described amount,
(B) The nitrogen-containing basic compound is used in an amount of 10 ^-6 to 10 ^-1 mol, particularly 10 ^-5 to ¹ mol, per 1 mol of the aromatic dihydroxy compound.
It is preferably used in an amount of 0 ² mol. (C) As boric acid or borate ester, the following general formula B (OR ³ ) _n '(OH) _3-n' (where R ³ is a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon A hydrogen group or an aromatic hydrocarbon group, and n ′ is 1 to
It is an integer of 3. Are preferred, and examples thereof include boric acid, trimethyl borate, triethyl borate,
Examples include tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tolyl borate, and trinaphthyl borate. Of these, triphenyl borate is particularly preferred. These (c) boric acid or boric acid ester of the above (a), when used as a catalyst with (b), the amount 10 ^-6 10 ^-1 mole relative to 1 mole of the aromatic dihydroxy compound, particularly 10 ^{- 5} to 1
Preferably it is 0 ^-2 mol.

The conditions such as temperature and pressure during the melt polymerization reaction are arbitrary, and known conditions can be used. Specifically, the first-stage reaction is preferably performed at 80 to 250.
C., more preferably 100 to 230C, particularly preferably 120 to 190C, preferably 0 to 5 hours, more preferably 0 to 4 hours, particularly preferably 0.25 to 3 hours.
Perform at normal pressure for hours. Next, the reaction temperature is increased while reducing the pressure of the reaction system to carry out the reaction between the aromatic dihydroxy compound and the carbonic acid diester. Finally, the aromatic dihydroxy compound is heated at a temperature of 240 to 320 ° C. under a reduced pressure of 0.05 to 5 mmHg. And the reaction of carbonic acid diester.

The reaction between the aromatic dihydroxy compound and the carbonic acid diester as described above may be carried out in a continuous manner or in a batch manner. Further, the reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

The component (A) thermotropic liquid crystal polyester used in the present invention can be selected from the group of polyesters containing a segment having the following structure.

--OR--O--CO--R--CO-- --OR--CO-- Here, each R can be selected from the group represented by the following formula.

[0044]

Embedded image Further, the aromatic ring, aliphatic group, alicyclic group, and the like in R may be substituted with a substituent selected from the group represented by the following formula.

[0045]

Embedded image (Wherein, R ¹ is an alkyl group or an aryl group having 1 to 40 carbon atoms, R ^{2 to} R ⁵ are a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, and these are the same, May also be different.)

The phosphonium sulfonate represented by the above general formula can be used for the resorcinol polycarbonate resin 1
0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, is added to 00 parts by weight. When the amount is less than 0.1 part by weight, a sufficient antistatic effect cannot be obtained, and when the amount is more than 10 parts by weight, transparency and mechanical strength are lowered, and the appearance of a molded article surface is unfavorably deteriorated.

R ¹ in the above general formula is an alkyl group or an aryl group, but an aryl group is more preferable from the viewpoints of transparency and heat resistance and the influence on the copolymerized polycarbonate resin.

Examples of the aryl group include groups derived from an alkylbenzene, an alkylnaphthalene ring and the like. Examples of these specific compounds include phosphonium dodecylsulfonate, phosphonium dodecylbenzenesulfonate and the like.

The method of blending the phosphonium sulfonate with the copolymerized polycarbonate resin can be carried out by various means at any stage immediately before molding the final molded article.

For example, the simplest method is to dry blend the copolymerized polycarbonate and the additive, and the dry blended product can be melt-extruded to form pellets.

Further, a master pellet containing a predetermined amount or more of additives is formed, and this is blended with a basic resin.
It can also be melt extruded. In any case, it is desirable to take care to make the dispersion of the additive good.

For the production of the final molded article from the copolymerized polycarbonate resin composition according to the present invention, ordinary molding means such as injection molding, extrusion molding, blow molding, compression molding and the like can be applied.

The copolycarbonate resin composition according to the present invention contains, in addition to the above additives, reinforcing agents such as glass fiber, carbon fiber, metal whiskers, carbon black, calcium carbonate, and glass beads. Such as fillers, lubricants such as paraffin wax and silicone oil, hindered phenols and other antioxidants, epoxy monomers, weathering agents such as triazines, and flame retardants such as halogen and phosphoric acid. And other well-known additives.

Other polycarbonates, polybutylene terephthalate, polyethylene terephthalate,
Various polymers such as polyethylene and polyethylene / propylene copolymer can also be used in combination.

[0055]

The present invention will be further disclosed below with reference to examples. In the table, "parts" indicates parts by weight.

The materials used in carrying out the glass fiber reinforced thermoplastic resin composition according to the present invention are as follows.

The polycarbonate PC (1) is a polycarbonate resin having a phenolic terminal group of less than 1%,
Lexan 141 (trademark; manufactured by General Electric) was used.

The polycarbonate PC (60) is 60%
LX polycarbonate having a phenolic end group and low end capping (trade name; Japan GE Plastics Co., Ltd.)
Manufactured).

As the liquid crystal polyester (LCP), Rodrun LC-5000 (trademark, manufactured by Unitika Ltd.) was used.

The following were used as the glass fibers. (1) GF-a Glass fiber obtained by compounding with epoxy as a sizing agent and using aminosilane as a binder, FES-03-1238DE (manufactured by Fuji Fiberglass Co., Ltd.) (2) GF-b EFS-03-1237B (Same as above), (3) GF-c FT121 (manufactured by Asahi Fiberglass Co., Ltd.)

The melt-kneading of polycarbonate, liquid crystal polyester, and glass fiber is performed by using a 30
Performed with a mm twin screw extruder. Extrusion conditions were set at a screw rotation speed of 150 rpm and a barrel temperature of 280 ° C. to produce pellets.

The following tests were performed to confirm the physical properties of the composition thus obtained. In conducting a test according to ASTM, a test piece was used with an 80 t injection molding machine manufactured by Toyo Kikai Metals Co., Ltd.
It was prepared at 0 ° C. and a mold temperature of 50 ° C.

The notched IZOD and flexural modulus are
Performed according to the standard ASTM method. In comparison with the comparative example using PC (1) as the polycarbonate, the component ratio of the composition and the test result of the example using the second polycarbonate PC (2) with low end capping are as shown in Table 1. is there.

[0064]

[Table 1] Comparative table of Examples and Comparative Examples

Incidentally, three types of glass fibers were used for each polycarbonate. As is clear from the test results, the second polycarbonate, PC (6
It can be seen that the composition containing 0) exhibits high flexural modulus and impact strength.

[0066]

The physical properties of a molded article obtained from the glass fiber reinforced thermoplastic resin composition according to the present invention are excellent in both impact resistance and flexural modulus as compared with conventional articles.

Because of these excellent physical properties, application to many uses can be expected.

Claims (2)

(57) [Claims] 1. A) 45 to 5 parts by weight of a thermotropic liquid crystal polyester resin; B) 40 to 5 parts of glass fibers and / or glass flakes.
Parts by weight, C) the equivalent ratio (I) / (II) of the phenolic terminal group (I) to the non-phenolic terminal group (II) is 1/19 or more;
A glass fiber-reinforced thermoplastic resin composition, comprising 15 to 90 parts by weight of a polycarbonate obtained by melt-polymerizing an aromatic dihydroxy compound and a carbonic acid diester. 2. The phenolic terminal group (I) has the following formula: And the non-phenolic end group (II) has the following formula: (Wherein R ¹ and R ² each independently represent a hydrogen atom, a straight-chain or branched, unsubstituted or halogen-substituted alkyl group having 20 or less carbon atoms). The resin composition as described in the above.